ES2567297T3 - Oil-in-water stabilized emulsions that include agriculturally active ingredients - Google Patents

Abstract

An oil-in-water emulsion composition having an oil phase and a water phase, the oil phase comprises: a polymer modifier that is compatible with the oil phase, in which the polymer modifier is ethyl cellulose; at least one agriculturally active compound; at least one nonionic lipophilic surfactant; at least one nonionic hydrophilic surfactant; at least one ionic surfactant.

Description

5

10

fifteen

twenty

25

30

35

40

Four. Five

DESCRIPTION

Oil-in-water stabilized emulsions that include agncolaly active ingredients References to related applications

The present application claims the benefit of the US provisional patent application for serial number 61 / 063,492, filed on February 4, 2008, and provisional US patent application for serial number 61 / 068,529, filed on March 7 of 2008, both are expressly incorporated by reference herein.

Field of the Invention

The present invention relates to compositions of agricultural emulsions of oil in water.

Background and compendium

Concentrated oil-in-water emulsions of active liquid ingredients or active ingredients dissolved in a solvent are commonly used in agricultural compositions because they provide certain advantages over other types of formulations. The emulsions are water based, contain little or no solvent, allow mixtures of active ingredients that are combined in a simple formulation and are compatible with a wide variety of packaging materials. However, there are also several disadvantages of such agricultural emulsions, namely that they are always complex formulations that require high amounts of surfactants for stabilization, are generally very viscous, have a tendency to maturity of Ostwald from the emulsion globules and separate with the weather. Therefore, improvements in such emulsion formulations in the agricultural field are needed.

Various oil-in-water emulsion compositions for cosmetic and dermatological applications have been described in US Patents 5,658,575; US 5,925,364; US 5,753,241; US 5,935,341; US 6,066,328; US 6,120,778; US 6,126,948; US 6,689,371; US 6,419,946; US 6,541,018; US 6.335022; US 6,274,150; US 6,375,960; US 6,464,990; US 6,413,527; US 6,461,625 and US 6,902,737; all are expressly incorporated by reference herein. However, although it has been found that these types of emulsions have advantageous use in personal care products, these types of emulsions have not previously been used with agncolaly active compounds, which are typically present in emulsions at much higher levels than active cosmetic ingredients. .

An example of an oil-in-water agricultural emulsion composition that is suitable for agncolaly active ingredients that are liquid or soluble in solvents suitable at relevant storage temperatures is described in U.S. Patent 2007/0027034 (U.S. Patent Application Number standard 11 / 495,228).

The present invention relates to agricultural compositions comprising an oil-in-water emulsion, the oil-in-water emulsion composition having an oil phase and water phase; the oil-in-water emulsion composition comprising an oil adapted to form oily globes having an average particle diameter of less than 800 nanometers, a polymeric modifier that is compatible with the oil phase, at least one agncolaly active compound, at less a non-ionic lipophilic surfactant, at least one non-ionic hydrophilic surfactant, at least one ionic surfactant, and water.

Detailed description

An embodiment of the present invention is a new oil-in-water emulsion composition having an oil phase and a water phase, the oil-in-water emulsion composition comprises:

an oil adapted to form oily globules having an average particle diameter of less than 800 nanometers;

a polymer modifier that is compatible with the oil phase, in which the polymer modifier is ethyl cellulose;

at least one agncolaly active compound; at least one non-ionic lipophilic surfactant; at least one non-ionic hydrophilic surfactant; at least one ionic surfactant; and water.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

The oil phase of the oil-in-water emulsion of the present invention uses either an agncolaly active compound that is in the form of an oil, or alternatively, an agncolaly active compound dissolved or mixed in an oil, to form the oily globule. . An oil is by definition, a liquid that is not miscible with water. Any oil that is compatible with the agncolaly active compound can be used in the oil-in-water emulsions of the present invention. The term "compatible" means that the oil is dissolved or mixed uniformly with the agncolaly active compound and allows the formation of oily globes of the oil-in-water emulsion of the present invention. Examples of oil include, but are not limited to, short chain fatty acid triglycerides, silicone oils, petroleum fractions or carbohydrates such as very aromatic naphthalene solvents, slightly aromatic naphthalene solvents, light hydrotreated oil distillates, solvents paraffin, mineral oil, alkyl benzenes, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, coconut oil, cottonseed oil, palm oil, soybean oil, and the like; alkylated vegetable oils and alkyl esters or fatty acids such as methyl oleate and the like.

An agncolaly active compound is defined herein as any oil soluble compound, hydrophobic compound, or solid compound having a melting point below about 95 degrees Celsius or less, showing some pesticidal or biocidal activity. It is understood that it refers to the active compound per se when it is itself an oil or alternatively, the active compound dissolved in a suitable oil or polymeric modifier. Such compounds or pesticides include fungicides, insecticides, nematocides, miticides, termiticides, rodenticides, arthrodicides, herbicides, biocides and the like. Examples of such agncolaly active ingredients can be found in The Pesticide Manual, 12th edition. Examples of pesticides that can be used in the oil-in-water emulsion of the present invention include, but are not limited to, benzofuranyl methylcarbamate insecticides such as benfuracarb, and carbosulfan; oxime carbamate insecticides such as aldicarb; fumigant insecticides such as chloropicrin, 1,3-dichloropropene and methyl bromide; juvenile hormone simulators such as fenoxicarb; organophosphate insecticides such as dichlorvos; aliphatic organothiophosphate insecticides such as malation and terbufos; aliphatic organothiophosphate amide insecticides such as dimethotate; benzotriazine organothiophosphate insecticides such as ethyl azinfos and methyl azinfos; organothiophosphate pyridine insecticides such as chlorpyrifos and methyl chlorpyrifos; organothiophosphate pyrimidine insecticides such as diazinon; phenyl organothiophosphate insecticides such as paration and methyl paration; pyrethroid ester insecticides, such as biphentrine, kyphlutrin, betaciflutrin, cyhalotrine, gamma cihalotrin, lambda cihalotrin, cypermethrin, alpha cypermethrin, beta cypermethrin, fenvalerate, and permethrin; and the like

Examples of herbicides that can be used in the oil-in-water emulsion of the present invention include, but are not limited to: amide herbicides such as dimetenamide and dimetenamide-P; anilide herbicides such as propanil; dichloroacetanilide herbicides such as acetochlor, alachlor, butachlor, metolachlor and S-metolachlor; oxime cyclohexane herbicides such as setoxidim; dinitroaniline herbicides such as benfluralin, etalfluralin, pendimethalin, and trifluralin; nitrile herbicides such as asbromoxynil octanoate; phenoxyacetic herbicides such as 4-CPA, 2, 4-D, 3, 4-DA, MCPA, and MCPA-thioethyl; phenoxybutmco herbicides such as 4-CPB, 2, 4-DB, 3, 4-DB, and MCPB; phenoxypropionic herbicides such as cloprop, 4-CPP, dichlorprop, dichlorprop-P, 3, 4-DP, fenoprop, mecoprop and mecoprop-P; aryloxy phenoxy propionic herbicides such as cihalofop, fluazifop, fluazifop-P, haloxifop, haloxifop-R; pyridine herbicides such as aminopiralid, clopiralid, fluroxypyr, picloram, and triclopyr; triazole herbicides such as ethyl carfentrazone; and the like

The herbicides can also generally be used in combination with known herbicide antidotes such as: benoxacor, cloquintocet, daimuron, dichlormid, diciclonon, fenclorazole, fenclorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-methylphen, methylphen-methylphen , MG191, MON4660, R29148, methanate, naphthalic anhydride, amides of N-phenyl sulfonyl benzoic acid and oxabetrinyl.

Examples of fungicides that can be used in oil-in-water emulsions of the present invention include, but are not limited to, diphenoconazole, dimetomorph, dinocarb, diphenylamine, dodemorf, ediphenphos, fenarimol, fenbuconazole, fenpropimorph, miclobutanyl, oleic acid (fatty acids ), propiconazole, tebuconazole and the like.

Those skilled in the art understand that any combination of agriculturally active compounds can also be used in the oil-in-water emulsion of the present invention provided that an active and effective emulsion is obtained.

The amount of agncolaly active ingredient in the water-in-oil emulsion will vary depending on the actual active ingredient, the application of the agncolaly active ingredient and the appropriate application levels that are well known to those skilled in the art. Typically, the total amount of agncolaly active ingredient in the oil-in-water emulsion will be about 1, generally about 5, preferably about 10, more preferably about 15 and most preferably about 20 to about 45, generally about 40, preferably at about 35 and most preferably at about 30 percent by weight based on the total weight of the oil-in-water emulsion.

The polymeric modifier can be included in the oil phase to retard the crystallization of the agncolaly active ingredient. The polymeric modifier allows the use of agncolamente active ingredients that have

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

melting points below about 95 degrees Celsius. Examples of such agncolaly active ingredients that can be used in the composition of the oil-in-water emulsion of the present description include Fluroxipir Meptil, Chlorpyrifos, Methyl Chlorpyrifos, Trifluralin, Cihalofop Butyl, Etalfluralin, Benfluralin, Miclobutanil, Acequinotr, Alfa-cipermetr Amitraz, Bensultap, Beta-ciflutrm, Beta-cipermetrm, Bifenox, Bifentrm, Bioresmetrm, Bromoxinyl octanoate, Butralin, Ciflufenamid, Ciflutrm, Cipermetrm, Diclofop-methyl, Dicofol, Esfenvalerate, Etalfluraphene-Phenopropane-Phepropropane-Phepropropane-Phepropropamine-Phepropropamine-Phepropropamine-Phepropropamine-Phenopropane-Phepropropane fenvalerate, flumiclorac-pentyl, ethyl fluoroglycofen, flurazole, Haloxyfop-etotil, indoxacarb, lambda-cihalotrm, metamifop, methoxychlor, Oxyfluorfen, pendimethalin, Permetrm, propaquizafop, pyributicarb, quizalofop-P-ethyl, Trifloxystrobin, Bromophos, Fenoxaprop-ethyl, Fluazolate, Nitrofen, and Profluralin.

Polymeric modifiers suitable for adding to the oil phase have very low water solubility and good solubility in a mixture of the active ingredient in a molten state with or without the presence of additional solvent. Examples of polymeric modifiers include ethyl cellulose, for example, Ethocel 10 Std FP, Ethocel Std 4, Ethocel Std 7, Ethocel 45, Ethocel 100 FP, and Ethocel 300.

The components of the oil-in-water emulsion are combined using a process described below to produce oily globules having a liquid crystal coating. The liquid crystal glass coating is an extremely thin mono or oligolaminar layer. It is understood that oligolaminar layer refers to a layer comprising 2 to 5 lipid sheets. This laminar liquid crystal coating can be detected by electron transmission microscopy after cryofracture or negative staining, X-ray diffraction or optical microscopy under polarized light. The terms and structure of the laminar liquid crystal phase are well defined in "The Colloidal Domain" second edition, by D. Fennell Evans and H. Wennerstrom, Wiley-VCH (1999), pages 295-296 and 306-307. The oligolaminar layer is composed of non-ionic lipophilic, non-ionic hydrophilic agents, and ionic surfactants, as previously indicated. Preferably, the lipophilic surfactant and the hydrophilic surfactant each contain at least one optionally saturated and / or branched fatty carbohydrate chain having more than 12 carbon atoms, preferably 16 to 22 carbon atoms.

Preferably, the lipophilic surfactant has an HLB between about 2 and about 5. HLB is a standard term known to those skilled in the art and refers to lipophilic hydrophilic equilibrium that identifies the solubility of the emulsifier in water or oil.

Lipophilus describes the ability of a material to dissolve in a fat or lipid solvent. The lipophilic surfactant is typically selected from optionally ethoxylated mono or polyalkyl ethers or esters of glycerol or polyglycerol, sorbitan mono or polyalkyl ethers or esters (optionally ethoxylated), mono or polyalkyl ethers or pentaerythritol, mono or polyalkyl ethers or esters of polyoxyethylene, and mono or polyalkyl ethers or esters of sugar. Examples of lipophilic surfactants include, but are not limited to, sucrose distearate, diglyceryl distearate, tetraglyceryl triestearate, decaglyceryl decaestearate, diglyceryl monostearate, hexaglyceryl triestearate, decaglyceryl penta stearate, sorbitan monostearate, sorbitanol stearateol glycerol, sorbitanol stearateol, sorbitanol steraterate and palmetic and stearic acids, polyoxyethylated monostearate 2 EO (containing 2 ethylene oxide units), glyceryl mono and dibehenate and pentaerythritol tetraestearate.

Hydrophilic describes the affinity of a material to associate with water. The hydrophilic surfactant typically has an HLB of about 8 to about 12 and typically are selected from mono or polyalkyl ethers or esters of polyethoxylated sorbitan, mono or polyalkyl ethers or esters of polyoxyethylene, mono or polyalkyl ethers or polyglycerol esters, block copolymers of polyoxyethylene with polyoxypropylene or polyoxybutylene, and mono or polyalkyl ethers or esters of optionally ethoxylated sugars. Examples of hydrophilic surfactants include, but are not limited to, polyoxyethylene sorbitan monostearate 4 EO, polyoxyethylene sorbitan triestearate 20, polyoxyethylene sorbitan triestearate 20, polyoxyethylene sorbitan monostearate, 8 polyoxyethylene sorbitan monostearate, polyethyleneterate monostearate, monostearate, ethostearate, polyoxyerate, polyoxyerate, polyoxyerate, polyoxyarate, ethostearate and methylglucose distearate 20 EO polyoxyethylene.

In addition to lipophilic and hydrophilic surfactants, an ionic surfactant also comprises the oligolaminar layer of the lamellar liquid crystal coating.

Ionic surfactants that can be used in the oil-in-water emulsion of the present invention include (a) neutralized anionic surfactants, (b) amphoteric surfactants, (c) alkylsulfonic derivatives and (d) cationic surfactants.

Neutralized anionic surfactants (a) include, but are not limiting, for example:

• alkali metal salts of dicetyl phosphate and dimiristyl phosphate, in particular sodium and potassium salts;

• alkali metal salts of cholesteryl sulfate and cholesteryl phosphate, especially sodium salts;

• lipoamino acids and their salts, such as mono and disodium acylglutamates, such as the disodium salt of

N-stearoyl-L-glutamic acid, the sodium salts of phosphatidic acid;

• phospholipids; Y

10

fifteen

twenty

25

30

35

• mono and disodium salts of acylglutamic acids, in particular N-stearoylglutamic acid.

Anionic surfactants chosen from alkyl ether citrates and mixtures thereof that can be used in oil-in-water emulsions of the present invention are described in US Patent 6,413,527, which is incorporated herein by reference. Alkyl ether citrates include monosters or diesters formed by dric acid and at least one oxyethylene fatty alcohol comprising a saturated or unsaturated, linear or branched alkyl chain having from 8 to 22 carbon atoms and comprising from 3 to 9 oxyethylenes groups, and their mixtures These citrates can be chosen, for example, from mono and diesters of citric acid and ethoxylated lauryl alcohol comprising from 3 to 9 oxyethylene groups. The alkyl ether citrates are preferably used in the neutralized form at a pH of about 7. Neutralizing agents can be chosen from inorganic bases, such as sodium hydroxide, potassium hydroxide or ammonium, and inorganic bases, such as mono, di , and trietolamine, aminomethyl-1,3-propanediol, N-methylglucamine, basic amino acids, such as arginine and lysine and mixtures thereof.

Amphoteric surfactants (b) include, but are not limited to, phosphoKpids and especially pure soy phosphatidyl ethanolamine.

Alkylsulfonic derivatives (c) include, but are not limited to, compounds of the formula:

R ---- CH ----- CO ---- O— (CH2CH20) 2 ----- CH3

so3m

wherein R represents the radicals C16H33 and C18H37, taken as a mixture or separately, and M is an alkali metal, preferably sodium.

The cationic surfactants (d) include, but are not limited to, surfactants as described in US Patent 6,464,990, which is incorporated herein by reference. Typically they are selected from the group of quaternary ammonium salts. Quaternary ammonium salts include, for example: those that show the following formula:

image 1

wherein the radicals R1 to R4, which may be identical or different, represent a linear or branched aliphatic radical comprising from 1 to 30 carbon atoms or an aromatic radical, such as aryl or alkylaryl. Aliphatic radicals may comprise heteroatoms, such as oxygen, nitrogen, sulfur or halogens. Aliphatic radicals include alkyl, alkoxy, polyoxy (C2-C6) alkylene, alkylamido, (C-12-C22) alkyl amido (C2-C6) alkyl acetate and hydroxyalkyl radicals comprising about 1 to 30 carbon atoms; X is an anion selected from halides, phosphates, acetates, lactates, (C2-C6) alkyl sulfates, and alkyl or alkylarylsulfonates. Preference is given, as quaternary ammonium salts to tetralkylammonium chlorides, such as dialkyl dimethyl ammonium and alkyltrimethylammonium chlorides in which the alkyl radical comprises about 12 to 22 carbon atoms, in particular behenyltrimethyl ammonium chlorides, distearyl dimethyl ammonium, cetyltrimethyl ammonium and benzyl dimethyltearyl ammonium or alternatively, stearamidopropyl dimethyl chloride (myristyl acetate); quaternary ammonium salts of imidazole, such as those of the formula:

image2

R8 +

CH— CH - N— CO - R5 ~ R7

X

wherein R5 represents an alkenyl or alkyl radical comprising from 8 to 30 carbon atoms, for example derived from tallow fatty acids; R6 represents a hydrogen atom, an alkyl radical comprising from 1 to 4 carbon atoms or an alkenyl or alkyl radical comprising from 8 to 30 carbon atoms; R7 represents an alkyl radical comprising from 1 to 4 carbon atoms; R8 represents a hydrogen atom or an alkyl radical comprising from 1 to 4 carbon atoms; and X is an anion selected from the group of halides, phosphates, acetates, lactates, alkyl sulfates, or alkyl, and alkylarylsulfonates. R5 and R6 preferably denote a mixture of alkenyl or alkyl radicals comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R7 preferably denotes a methyl radical and R8 preferably denotes hydrogen. Quaternary ammonium salts are also contemplated, such as tallow propane diamonium dichloride.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

Fatty amines include, but are not limited to, those of the formula:

R9 (CONH) n (CH2) mN (Rl 1) R10

wherein R9 is an optionally saturated and / or branched carbohydrate chain, having between 8 and 30 carbon atoms, preferably between 10 and 24 carbon atoms; R10 and R11 are selected from H and an optionally saturated and / or branched carbohydrate chain, having between 1 and 10 carbon atoms; preferably between 1 and 4 carbon atoms;

m is an integer between 1 and 10 and preferably is between 1 and 5; and n is either 0 or 1.

Examples of fatty amines include, but are not limited to, stearylamine, aminoethyl ethanolamide stearate, diethyl enetriamine stearate, palmitamido propyl dimethyl amine, palmitamido propyl diethyl amine, palmitamido ethyl diethyl amine, palmitamido ethyl dimethyl amine. Commercially available fatty amines include, but are not limited to, Incromine ™ BB from Croda, Amidoamine ™ MSP from Nikkol, and Lexamine ™ series from Inolex, the Acetamine series from Kao Corp; Berol 380, 390, 453 and 455, and Ethomeen ™ series from Akzo Nobel, and Marlazin ™ L10, OL2, OL20, T15 / 2, T50 from Condea Chemie.

As described above, the surfactants form the laminar liquid crystal coating of the oily globes in suspension in the aqueous phase of the oil-in-water emulsion of the present invention. The amount of the three surfactants used in the oil-in-water emulsion of the present invention is typically from about 20, preferably from about 35 to about 65, preferably from about 55 percent by weight of lipophilic non-ionic surfactant, of about 15, preferably from about 25 to about 50, preferably from about 40 percent by weight of hydrophilic non-ionic surfactant and from about 5, preferably from about 10 to about 45, preferably from about 35 percent by weight of ionic surfactant; based on the total combined weight of the surfactants. The coating of oily globules comprises a total amount of hydrophilic surfactant, lipophilic surfactant and ionic surfactant that is between about 2 and about 20 percent by weight, based on the total weight of the oil-in-water emulsion. Preferably the total amount is about 2.5, more preferably about 3 to 10, more preferably about 6 percent by weight, based on the total weight of the oil-in-water emulsion.

The ratio between the total weight of the surfactant compounds and the total oil weight is typically 1: 2.5 to 1:25.

The amount of polymeric modifier used in the oil-in-water emulsion of the present description is typically from about 0.2, preferably from about 2 to about 40, preferably from about 20 percent by weight based on the total weight of the emulsion of oil in water

The aqueous phase is typically water, for example, deionized water. The aqueous phase may also contain other additives such as compounds that lower the freezing point, for example alcohols, e.g. ex. isopropyl alcohol and propylene glycol; pH buffering agents, for example alkali phosphates such as sodium monobasic sodium phosphate monohydrate, dibasic sodium phosphate; biocides, for example Proxel GXL; and antifoams, for example octamethyl cyclootetra siloxane (Dow Corning Antifoam A). Other additives and / or adjuvants may also be present in the aqueous phase as long as the stability of the oil-in-water emulsion is maintained. Other additives may also include water soluble agriculturally active compounds.

The oil phase or the coating of oily globules are 5, preferably 8 and more preferably 10 to 50 percent, preferably 45 and most preferably 40 percent by weight, based on the total weight of the composition of oil in water emulsion. The oil / water ratio is typically less than or equal to 1.

Other additives and / or adjuvants may also be present in the oil-in-water emulsion of the present invention, provided that the stability and activity of the oil-in-water emulsion is obtained. The oil-in-water emulsion of the present invention may additionally contain adjuvant surfactants to improve the deposition, wetting and penetration of the agriculturally active ingredient on the target site, e.g. ex. harvest, weed or organism. These adjuvant surfactants can optionally be used as an emulsion component either in the water oil phase, or as a tank mixing component; The use of a desired amount is well known to those skilled in the art. Suitable adjuvant surfactants include, but are not limited to, ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines and combinations of surfactants with vegetable or mineral oils.

The oil-in-water emulsion of the present invention can be prepared according to the process described in US Patent 5,925,364, the conclusions of which are incorporated herein by reference. The ingredient

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

agncolamente active or a combination of agncolamente active ingredients are first melted or dissolved in the polymer modifier, adding solvent if desired, after which the non-ionic surfactant (s) is dissolved in the mixture. The mixture is then homogenized by cavitation using a high pressure homogenizer, to provide the small particle size oily globes. The average size of the coated oil globes is typically less than 800 nanometers, preferably less than 500 nanometers and most preferably approximately 200 nanometers, as determined using particle size analysis by laser diffraction and electron scanning microscopy.

In one embodiment, the oil-in-water emulsion is prepared:

1) melt or dissolve an agncolamente active ingredient (s) in the polymeric modifier and optionally a suitable solvent;

2) mixing an oil phase, comprising lipophilic surfactant, the polymeric modifier contains the dissolved agncolaly active ingredient (s), the hydrophilic surfactant, the ionic surfactant, an agncolaly active compound and optionally a suitable solvent and (B) a phase of water to obtain a mixture; Y

3) homogenize the mixture by subjecting the mixture to cavitation.

In the first stage, the mixture can be formed by conventional stirring, for example, using a high shear homogenizer that rotates at a speed of approximately 2,000 to 7,000 rpm for a time between approximately 5 and 60 minutes and at a temperature between approximately 20 ° C and 95 ° C.

Homogenization can be carried out using a high pressure homogenizer that works at pressures between approximately 200 and 1,000 bar as those skilled in the art know. The process is carried out in successive stages, generally from 2 to 12 stages, at a selected pressure; the mixture returns to normal pressure between each stage. The homogenization of the second step can also be carried out under the action of ultrasound or alternatively by using a homogenizer equipped with a rotor-stator type head.

Another embodiment of the present invention in the use of oil-in-water emulsion in agricultural applications to control, avoid or eliminate unwanted living organisms, e.g. ex. fungi, weeds, insects, bacteria or other microorganisms and other pests. This includes its use to protect a plant against the attack of a phytopathogenic organism or the treatment of a plant already infested by a phytopathogenic organism, which comprises applying the emulsion composition of oil in water, to the soil, a plant, a part of a plant, leaves, flowers, fruit, and / or seeds in an amount that inhibits a disease and is phytologically acceptable. The term "amount that inhibits a disease and phytologically acceptable" refers to an amount of a compound that kills or inhibits the disease of the plant to be controlled, but is not significantly toxic to the plant. The exact concentration of the required active compound varies with the fungal disease to be controlled, the type of formulations used, the particular plant species, weather conditions, and the like, as is known in the art.

Additionally, oil-in-water emulsions of the present invention are useful for the control of insects or other pests, e.g. ex. rodents Therefore, the present invention is also directed to a method for inhibiting an insect or pest that comprises the application to an insect or pest part of an oil-in-water emulsion comprising an insect inhibitory amount of an agncolaly active component for such use. The "part" of insects or pests is a term used herein that refers to the environment in which insects or pests live or where their eggs are, including the air around them, the food they eat, or objects with those who contact. For example, insects that eat or come into contact with edible or ornamental plants can be controlled by applying the active compound to plant parts such as seed, planting, or cutting what is planted, leaves, stems, fruits, grain, or roots, or the soil on which the roots grow. It is contemplated that agncolaly active compounds and oil-in-water emulsions that contain them, may also be useful for protecting textiles, paper, stored grain, seeds, pets, buildings or humans by applying an active compound on or near such objects. The term "inhibit an insect or pest" refers to a decrease in the number of live insects or pests, or a decrease in the number of viable insect eggs. The extent of the reduction achieved by a compound depends, of course, on the degree of application of the compound, the compound used in particular, and the species of insect or target pest. At least one inactivating amount should be used. The term "inactivating amount of insect or pest" is used to describe the amount, which is sufficient to cause a measurable reduction in the treated insect or pest population, as is known in the art.

The site where the compound or composition is applied can be any site inhabited by an insect, mite or pest, for example, vegetable crops, fruits and walnuts, vineyards, ornamental plants, pets, interior or exterior surfaces of buildings, and The ground around buildings.

Due to the unique ability of insect eggs to resist toxic action, repeated applications to control newly emerged larvae may be desirable, as is known from other known insecticides and acaricides.

5

10

fifteen

twenty

25

30

35

40

Additionally, the present invention relates to the use of water-in-oil emulsions comprising agncolaly active compounds that are herbicides. The term herbicide is used herein to designate an active ingredient that kills, controls or does not adversely modify plant growth. An effective amount of herbicide or vegetation control is an amount of active ingredient that causes an adverse modifying effect and that includes deviations from natural development, killing, regulating, drying out, retarding or the like. The terms plants and vegetation include emerged seeds and established vegetation.

Herbicidal activity is shown when applied directly to the site of the undesirable plant at any stage of growth or before the emergence of the weed. The observed effect depends on the species of plant to be controlled, the state of growth of the plant, the particle size of the solid components, the environmental conditions at the time of use, the specific adjuvants and bonds used, the type of soil, and similar, as well as the amount of chemical applied. These and other factors can be adjusted as is known in the art to promote selective herbicide action. Generally, it is preferred to apply such post-emergence herbicides to relatively immature undesirable vegetation to achieve maximum weed control.

Another specific aspect of the present invention is a method of avoiding or controlling pests such as nematodes, mites, arthropods, rodents, termites, bacteria or other microorganisms, which comprises applying a composition of the present to a site where control or prevention is desired. invention comprising the appropriate active component such as a nematicide, acaricide, arthropodicide, rodenticide, termiticide or biocide.

The actual amount of agncolaly active compound to be applied to the site or disease, insects and mice, weeds or other pests is known in the art and can be quickly determined by those skilled in the art in view of the foregoing conclusions.

The composition of the present invention surprisingly offers agriculturally stable oil-in-water emulsions that have low viscosity and long service life. Additionally, agriculturally stable oil-in-water emulsions of the present invention may offer other surprising improvements, e.g. ex. effectiveness.

The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be construed ast. The amounts are parts by weight or percentages by weight unless otherwise indicated.

Examples

These examples are provided to further illustrate the invention and are not intended to be construed as limiting.

As described herein, all temperatures are given in degrees Celsius and all percentages are weight percentages unless otherwise indicated. The active ingredients of all examples are supersaturated.

In these examples, the process is carried out using the following procedure:

The solid agncolaly active ingredient melts or dissolves in the polymeric modifier. The polymer modifier is then mixed in the oil phase A. The oil phase A and the water phase B are heated separately to the desired temperature. Phase B is poured over phase A, with stirring at 4,000-8,000 rpm provided by a Silverson L4RT high shear homogenizer coupled with a square hole high shear filter. Stirring and temperature conditions are maintained for 10 minutes.

The mixture is then introduced into a 2-stage high pressure homogenizer Niro Soavi of the Panda 2K type, which is adjusted to a pressure of 1,000 bar for 2 to 12 successive stages.

In this way an oil-in-water emulsion is obtained, whose oily globes have an average diameter

Typically around 200 nm.

Example 1: oil emulsion in fluoxipir MHE water

Phase A of water% by weight

Fluoxipir methyl heptyl ester 27.29

Etocel 10 Std FP 2.73

Diglycerol monostearate (Nikkol DGMS from Nikko Chemical Co.) 2.70

Sorbitan (40EO) stearate (Uniqema Tween 61) 2.03

Oil (AMD 810) 12.12

 B phase of water

 Deionized water

 42.30

 Biocide Proxel GLX

 0.10

 Cedepal TD-407

 0.73

 Glycerin

 10.00

The samples showed no sign of crystal formation, creaminess or sediment after 10 weeks at 0 ° C at room temperature. The size of the oil globules in the oil-in-water emulsion as determined by Malvern Zetasizer was 242 nm. The oil-in-water emulsion was stable under accelerated storage conditions of 10-week freeze / fusion test (the daily temperature cycle from -10 ° C to 40 ° C) and 54 ° C without 5 change in the size of the oily globules without sedimentation or syneresis.

Example 2: oil emulsion in fluoxipir MHE water

 Water phase A

 % in weigh

 Fluoxipir methyl heptyl ester

 27.29

 100FP Etocel

 2.73

 Diglycerol monostearate (Nikkol DGMS from Nikko Chemical Co.)

 2.70

 Sorbitan (40EO) stearate (Tween 61 from Uniqema)

 2.03

 Oil (AMD 810)

 12.12

 B phase of water

 Deionized water

 48.30

 Biocide Proxel GLX

 0.10

 Cedepal TD-407

 0.73

 Propylene glycol

 4.00

The size of the oil globules in the oil-in-water emulsion as determined by Malvern Zetasizer was 410 nm. The samples showed no sign of crystal formation, creaminess or sediment after 10 weeks at 0 ° C at room temperature. The oil-in-water emulsion was stable under accelerated storage conditions of 10 weeks freeze / melt test (the daily temperature cycle from -10 ° C to 40 ° C) and 54 ° C without

change in the size of the oily globules and without sedimentation or syneresis.

Example 3: emulsion of oil in water fluoxipir MHE

Phase A of water% by weight

Fluoxipir methyl heptyl ester 25.9

Etocel Std 7 2.6

Diglycerol monostearate (Nikkol DGMS from Nikko Chemical Co.) 2.6

Sorbitan (40EO) stearate (Uniqema Tween 61) 1.9

Oil (AMD 810) 11.5

B phase of water

Deionized Water 54.2

Sodium phosphate, dibasic 0.3

Sodium phosphate, monobasic monohydrate 0.2

Biocide Proxel GLX 0.3

Disodium salt of glutamic acid n-stearoyl (Amisoft HS-21P 0.5

Ajinomoto)

The samples showed no sign of crystal formation, creaminess or sediment after 10 weeks at 0 ° C at room temperature. The size of the oil globules in the oil-in-water emulsion as determined by Malvern Zetasizer was 190 nm. The oil-in-water emulsion was stable under accelerated test storage conditions of 2 weeks at room temperature, and 54 ° C without change in the size of the oil globules 5 and without sedimentation or syneresis.

Example 4: oil emulsion in trifluralm water

 Water phase A

 % in weigh

 Trifluralm

 24.0

 Etocel Std 4

 2.4

 Diglycerol monostearate (Nikkol DGMS from Nikko Chemical Co.)

 2.6

 Sorbitan (40EO) stearate (Tween 61 from Uniqema)

 1.9

 Genigen 4166

 9.6

 B phase of water

 Deionized water

 51.2

 Disodium salt of glutamic acid n-stearoyl (Amisoft HS-21P from Ajinomoto)

 0.5

 Biocide Proxel GLX

 0.3

 1,2-propanediol

 7.5

The samples showed no sign of crystal formation, creaminess or sediment after two weeks at room temperature. The size of the oil globules in the oil-in-water emulsion as determined by Malvern Zetasizer was 185 nm. The oil-in-water emulsion was stable under accelerated storage conditions for a 2-week test at 40 ° C and 54 ° C without change in the size of the oil globes and without sedimentation or syneresis.

Example 5: emulsion of oil and water chlorpyrifos

 Water phase A

 % in weigh

 Chlorpyrifos

 10.0

 Etocel 4S

 1.0

 Genigen 4166

 2.4

 Sorbitan (40EO) stearate (Tween 61 from Uniqema)

 1.5

 Stearil ether PEG 2

 2.0

 B phase of water

 Deionized water

 82.6

 Disodium salt of glutamic acid n-stearoyl (Amisoft HS-21P from Ajinomoto)

 0.5

The samples showed no sign of crystal formation, creaminess or sediment after two weeks at room temperature. The size of the oil globules in the oil-in-water emulsion as determined by Malvern Zetasizer was 190 nm. The oil-in-water emulsion was stable under accelerated test storage conditions of 2 weeks at 40 ° C and 54 ° C without change in the size of the oil globes and without sedimentation or syneresis.

Example 6: emulsion of oil and water chlorpyrifos

 Water phase A

 % in weigh

 Chlorpyrifos

 20.0

 Etocel 4S

 2.0

 Genigen 4166

 4.8

 Sorbitan (40EO) stearate (Tween 61 from Uniqema)

 1.7

 Stearil ether PEG 2

 2.3

 B phase of water

 Deionized water

 61.1

 Disodium salt of glutamic acid n-stearoyl (Amisoft HS-21P from Ajinomoto)

 0.6

 1,2-peopylene glycol

 7.5

The samples showed no sign of crystal formation, creaminess or sediment after two weeks at room temperature. The size of the oil globules in the oil-in-water emulsion as determined by Malvern Zetasizer was 190 nm. Accelerated test storage conditions of 2 weeks at 40 ° C 5 led to a slight increase in the size of the oil globes at 200 nm.

Claims (14)

5 10 fifteen twenty 25 30 35 40 Four. Five 1. An oil-in-water emulsion composition having an oil phase and a water phase, the oil phase comprises: a polymer modifier that is compatible with the oil phase, in which the polymer modifier is ethyl cellulose; at least one agncolaly active compound; at least one non-ionic lipophilic surfactant; at least one non-ionic hydrophilic surfactant; at least one ionic surfactant. 2. The composition of claim 1, wherein the non-ionic lipophilic surfactant has a lipophilic hydrophilic balance between 2 and 5. 3. The composition of claim 2, wherein the non-ionic lipophilic surfactant is selected from the group consisting of mono or polyalkyl ethers or esters of glycerol or polyglycerol, mono or polyalkyl ethers or esters of sorbitan, mono or polyalkyl ethers or esters of pentaerythritol, mono or polyalkyl ethers or esters of polyoxyethylene, and mono or polyalkyl ethers or esters of sugar. 4. The composition of claim 3, wherein the non-ionic lipophilic surfactant is selected from the group consisting of sucrose distearate, diglyceryl distearate, tetraglyceryl triestearate, decaglyceryl decaestearate, diglyceryl monostearate, hexaglyceryl triestearate, decaglyceryl pentaarate monostearate, monostearate sorbonate, monostearate sorbonate , sorbitan triestearate, diethylene glycol monostearate, glycerol ester and palmetic and stearic acids, polyoxyethylated monostearate 2 EO (containing 2 ethylene oxide units), glyceryl mono and dibehenate and pentaerythritol tetraestearate. 5. The composition of claim 1, wherein the non-ionic hydrophilic surfactant has a lipophilic hydrophilic balance between 8 and 12. 6. The composition of claim 5, wherein the non-ionic hydrophilic surfactant is selected from the group consisting of mono or polyalkyl ethers or esters of polyethoxylated sorbitan, mono or polyalkyl ethers or esters of polyoxyethylene, mono or polyalkyl ethers or esters of polyglycerol, block copolymers of polyoxyethylene with polyoxypropylene or polyoxybutylene, and mono or polyalkyl ethers or esters of sugars. 7. The composition of claim 6, wherein the non-ionic hydrophilic surfactant is selected from the group consisting of polyoxyethylene sorbitan monostearate 4 EO, polyoxyethylene sorbitan triestearate 20, polyoxyethylene sorbitan triestearate 20 EO polyoxyethylene sorbitan monostearate , hexaglyceryl monostearate, monostearate 10 EO polyoxyethylene, distearate 12 EO polyoxyethylene and methylglucose distearate 20 EO polyoxyethylene. 8. The composition of claim 1, wherein the ionic surfactant is selected from the group consisting of (a) neutralized anionic surfactants, (b) amphoteric surfactants, (c) alkyl sulfonic derivatives and (d) cationic surfactants . 9. The composition of claim 8, wherein the ionic surfactant is selected from the group consisting of: - alkali metal salts of dicetyl phosphate and dimiristyl phosphate, in particular sodium and potassium salts; - alkali metal salts of cholesteryl sulfate and cholesteryl phosphate, especially sodium salts; - lipoamino acids and their salts, such as mono and disodium acylglutamates, such as the disodium salt of N-stearoyl-L-glutamic acid, the sodium salts of phosphatidic acid; - phospholipids; - mono and disodium salts of acylglutamic acids, in particular N-stearoylglutamic acid. - alkyl ether citrates. 10. The composition of claim 8, wherein the ionic surfactant is (a) a phospholipid, (b) an alkylsulfonic derivative, or (c) a compound selected from the group consisting of quaternary ammonium salts, amines Acids and their salts. 11. The composition of claim 1, wherein the agncolamente active compound is selected from the group consisting of fungicides, insecticides, nematocides, miticides, biocides, termiticides, rodenticides, arthrodicides and herbicides. 12. The composition of the claim, wherein the composition of the oil-in-water emulsion is from 1 to 5 60 percent by weight of the total oil phase, from 0.2 to 40 percent by weight of polymeric modifier, from 1 to 45 per one hundred by weight of agncolaly active compound, from 0.4 to 13 percent by weight of non-ionic lipophilic surfactant, from 0.3 to 10 percent by weight of non-ionic hydrophilic surfactant, from 0.1 to 9 percent by weight of ionic surfactant, based on the total weight of the oil-in-water emulsion composition. 13. A method to prevent or control fungi, insecticides, nematodes, arachnids, arthropods, rodents, 10 termites, bacteria and other microorganisms, which includes applying to a site where control or prevention is desired. a composition of claim 11, wherein said site is not a human or an animal. 14. A method for avoiding or controlling unwanted vegetation, which comprises applying a composition of claim 11 to a site where control or prevention is desired.